Nickel positive electrode material comprising rare earth minerals

ABSTRACT

An active material mixture for use in a paste for fabricating positive electrodes, comprising a nickel hydroxide material, and an additive material comprising at least one material selected from the group consisting of a rare earth mineral, and a rare earth concentrate. A nickel positive electrode and an alkaline electrochemical cell using this active material mixture.

FIELD OF THE INVENTION

The present invention relates to an improved positive electrodematerial, to a nickel positive electrode using the electrode material,and to an alkaline electrochemical cell using the nickel positiveelectrode.

BACKGROUND OF THE INVENTION

The recent trend for portable apparatus has increased the requirementfor high energy density rechargeable batteries. High energy density isalso important for batteries used for electric vehicles.

Nickel hydroxide has been used for years as an active material for thepositive electrode of alkaline electrochemical cells. Examples of suchnickel-based alkaline cells include nickel cadmium (Ni--Cd) cells andnickel-metal hydride (Ni-MH) cells. The energy density of suchnickel-based electrochemical cells may be increased by closely packingthe nickel hydroxide active material into an electrically conductivesubstrate such as a porous foam. However, there are limitations on theamount of pressure used to increase packing density. Application of toomuch pressure causes expansion of electrode plates and compresses theseparators placed between the positive and negative electrodes. Thecompression of the separators presses out the electrolyte solution anddeteriorates the discharge characteristics.

In a nickel cadmium cell, cadmium metal is the active material in thenegative electrode. Ni--Cd cells use a positive electrode of nickelhydroxide material. The negative and positive electrodes are spacedapart in the alkaline electrolyte. The charge/discharge reactions at thenegative electrode are controlled by the following reaction: ##EQU1##

During charge, electrons are supplied to the negative electrode, wherebyCd(OH)₂ is reduced to Cd. During discharge, Cd is oxidized to Cd(OH)₂and electrons are released.

The reactions that take place at the positive electrode of a Ni--Cd cellare also reversible. For example, the reactions at a nickel hydroxidepositive electrode in a nickel cadmium cell are: ##EQU2## At thepositive electrode, Ni(OH)₂ is oxidized to NiOOH during the chargeoperation. During discharge, the NiOOH is reduced to Ni(OH)₂.

In general, nickel-metal hydride (Ni-MH) cells utilize a negativeelectrode comprising a metal nydride active material that is capable ofthe reversible electrochemical storage of hydrogen. Examples of metalhydride materials are provided in U.S. Pat. Nos. 4,551,400, 4,728,586,and 5,536,591 the disclosures of which are incorporated by referenceherein. The positive electrode of the nickel-metal hydride cell comprisea nickel hydroxide active material. The negative and positive electrodesare spaced apart in the alkaline electrolyte.

Upon application of an electrical potential across a Ni-MH cell, theNi-MH material of the negative electrode is charged by theelectrochemical absorption of hydrogen and the electrochemicalgeneration of hydroxyl ions: ##EQU3## The negative electrode reactionsare reversible. Upon discharge, the stored hydrogen is released to forma water molecule and evolve an electron.

The reactions that take place at the nickel hydroxide positive electrodeof a Ni-MH cell are the same as for a Ni--Cd cell and are provided byreaction (2).

Hence, the charging process for a nickel hydroxide positive electrode inan alkaline storage battery is governed by the following reaction:##EQU4##

The charging efficiency of the positive electrode and the utilization ofthe positive electrode material is affected by the oxygen evolutionprocess which is controlled by the reaction:

    2OH--→H.sub.2 O+1/2O.sub.2 +2e-                     (5)

During the charging process, a portion of the current applied to thebattery for the purpose of charging, is instead consumed by the oxygenevolution reaction (5). The oxygen evolution of reaction (5) is notdesirable and contributes to lower utilization rates upon charging. Onereason both occur is that their electrochemical reaction potentialvalues are very close. Anything that can be done to widen the gapbetween them (i.e., lowering the nickel reaction potential is reaction(4) or raising the reaction potential of the oxygen evolution reaction(5)) will contribute to higher utilization rates. It is noted that thereaction potential of the oxygen evolution reaction (5) is also referredto as the oxygen evolution potential.

Furthermore, the electrochemical reaction potential of reaction (5) istemperature dependent. At lower temperatures, oxygen evolution is lowand the charging efficiency is high. However, at higher temperatures,the electrochemical reaction potential of reaction (5) decreases and therate of the oxygen evolution reaction (5) increases so that the chargingefficiency of the nickel hydroxide positive electrode drops. Hightemperatures at the positive electrodes may be due to the externalenvironment at which the battery is operated. They may also be due tothe heat generated within the battery by oxygen gas recombination at thenegative electrodes.

One way to increase the reaction potential of equation (5) is by mixingcertain additives with the nickel hydroxide active material when formingthe positive electrode paste. U.S. Pat. Nos. 5,466,543, 5,451,475 and5,571,636 disclose certain additives which improve the rate ofutilization of the nickel hydroxide in a wide temperature range. Thepresent invention discloses new additives which improve the hightemperature utilization of nickel-based positive electrode materials.

SUMMARY OF THE INVENTION

An objective of the present invention is a positive electrode activematerial mixture, a nickel positive electrode, and an alkalineelectrochemical cell having high-temperature capacity and utilization.

This objective is further satisfied by an active material mixture foruse in a paste for fabricating positive electrodes, comprising: a nickelhydroxide material; and an additive material comprising at least onematerial selected from the group consisting of a rare earth mineral, anda rare earth concentrate.

This objective is further satisfied by an active material mixture foruse in a paste for fabricating positive electrodes, comprising: a nickelhydroxide material; and an additive material comprising at least onematerial selected from the group consisting of a misch metal, and amisch metal alloy.

This objective is further satisfied by a nickel positive electrode foran alkaline electrochemical cell, comprising: an active material mixturecomprising: a nickel hydroxide material; and an additive materialcomprising at least one material selected from the group consisting of arare earth mineral, and a rare earth concentrate.

This objective is further satisfied by a nickel positive electrode foran alkaline electrochemical cell, comprising: an active material mixturecomprising: a nickel hydroxide material; and an additive materialcomprising a material selected from the group consisting of a mischmetal, and a misch metal alloy.

This objective is further satisfied an alkaline electrochemical cell,comprising: at least nickel positive electrode; at least one negativeelectrode; and electrolyte; where the positive electrode comprises anactive material mixture comprising: a nickel hydroxide material; and anadditive material comprising at least one element selected from thegroup consisting of a rare earth mineral, and a rare earth concentrate.

This objective is further satisfied by an alkaline electrochemical cell,comprising: at least nickel positive electrode; at least one negativeelectrode; and electrolyte; where the positive electrode comprises anactive material mixture comprising: a nickel hydroxide material; and anadditive material comprising at least one element selected from thegroup consisting of a misch metal, and a misch metal alloy.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein is a positive electrode active material mixture for usein a paste for fabricating positive electrodes. The active materialmixture comprises a nickel hydroxide material and an additive material.

In one embodiment, the additive material comprises at least one materialselected from the group consisting of a rare earth mineral, and a rareearth concentrate. In general, a rare earth mineral is a mineralcomprising at least one rare earth element. As used herein, the term"rare earth element" refers to the elements Y, La, Ce, Pr, Nd, Pm, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. As used herein, the term"lanthanides" refers to the elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,Dy, Ho, Er, Tm, Yb, and Lu. (That is, the term "lanthanides" includesall of the elements listed under "rare earth elements" except for Y(yttrium)).

In general, any rare earth mineral may be used as the additive material.Preferably, the rare earth mineral is selected from the group consistingof bastnasite, monazite, loparite, xenotime, apatite, eudialyte, andbrannerite. More preferably, the rare earth mineral is bastnasite, ormonazite. Other examples are provided in the book Rare EarthMinerals--Chemistry, Origin and Ore Deposits, Chapman and Hall, 1996.The rare earth mineral may be heat treated before being mixed with thenickel hydroxide material. Mixtures of rare earth minerals may also beused.

The additive material may comprise a rare earth concentrate. A rareearth concentrate is a material derived directly from processesoperating on the starting rare earth mineral before any separation intoeither individual rare earth elements or individual rare earth compoundstakes place. Typically, the rare earth mineral is treated byconventional mineral processing technology, such as comminution followedby froth flotation, to produce the rare earth concentrate. Preferably,the rare earth concentrate is selected from the group consisting ofbastnasite concentrate, monazite concentrate, loparite concentrate,xenotime concentrate, apatite concentrate, eudialyte concentrate, andbrannerite concentrate. More preferably, the rare earth concentrate isbastnasite concentrate, or monazite concentrate. Mixtures of rare earthconcentrates may also be used.

Many rare earth concentrates may be split into other concentrates whichare rich in certain of the rare earth elements. For example, bastnasiteconcentrate may be split into two other concentrates. One is calledlanthanum concentrate and the other is called cerium concentrate. Thelanthanum concentrate contains only a small percentage of cerium whilethe cerium concentrate is cerium rich. It is noted that concentratesderived from other concentrates are included within the concept of "rareearth concentrate" are used herein and are also within the scope of thisinvention.

It is noted that U.S. Pat. Nos. 5,571,636 and 5,451,475 disclose theaddition of yttrium, or a powdery compound of yttrium such as yttriumoxide or yttrium carbonate to the nickel hydroxide material. Also, U.S.Pat. No. 5,466,543 discloses a nickel hydroxide material containing atleast one compound of yttrium. It is noted that rare earth minerals andrare earth concentrates are not pure rare earth elements or pure rareearth compounds, and that the '475, '636 and '543 Patents fail to eitherteach or suggest that either a rare earth mineral or a rare earthconcentrate can be added to the active nickel hydroxide material toimprove the high temperature utilization.

In another embodiment of the present invention, the additive material isat least one material selected from the group consisting of misch metal,and misch metal alloy. As used herein misch metal may be denoted as"Mm". A "misch metal" is defined herein as a mixed rare earth metal. Itmay be prepared by electrolysis of fused rare earth chlorides. Mischmetals may comprise between about 94 to 99% rare earth metals plustraces of aluminum, calcium, carbon, silicon, and iron. An example of amisch metal composition is between about 50 to 60% cerium, between about25 to 30% lanthanum, between about 15 to 17% neodymium, and betweenabout 4 to 6% praseodymium.

The misch metal alloy may comprise nickel. An example of a misch metalalloy is a nickel-based misch metal alloy such as MmNi_(x), where x isbetween about 4.5 and about 5.5.

Preferably, the additive material is between about 1% and 10% by weightof the positive electrode active material mixture. More preferably, theadditive material is between about 2% and 6% by weight of the positiveelectrode active material mixture. Most preferably, the additivematerial is about 3% by weight of the positive electrode active materialmixture.

The nickel hydroxide material may be any nickel hydroxide material knownin the art. It is within the spirit and intent of this invention thatany and all kinds of nickel hydroxide materials may be used. Examples ofpossible nickel hydroxide materials are provided in U.S. Pat. Nos.5,348,822 and 5,637,423, the contents of which are incorporated byreference herein.

Also disclosed herein is a nickel positive electrode for use in analkaline electrochemical cell. The nickel positive electrode comprisesthe active material described above. The positive electrode furthercomprises an electrically conductive substrate used to support theactive material. The electrically conductive substrate may be anysubstrate, known in the art, capable of holding the positive electrodematerial. It is within the spirit and intent of this invention that anyand all kinds of electrically conductive substrates may be used.Examples of substrates include foam, perforated metal, expanded metal,screen, and matte. Preferably the substrate is a metal foam. Preferably,the metal comprises nickel or a nickel alloy.

The additive materials are mixed with the nickel hydroxide material toform the active material mixture. Preferably, a binder, such aspolyvinyl alcohol, is also added to the active material mixture to forma paste. The paste is affixed to an electrically conductive substrate toform the electrode.

It is noted that the additive material serves as a poison for the oxygenevolution reaction (5). As a result, a charge reaction of nickelhydroxide to nickel oxyhydroxide expressed as reaction formula (4)sufficiently proceeds to improve the utilization of the nickel positiveelectrode in the high-temperature atmosphere.

Also disclosed herein is an alkaline electrochemical cell. Theelectrochemical cell comprises at least one nickel positive electrode,at least one negative electrode, and electrolyte. The positive electrodeis the positive electrode described above comprising the active materialmixture of the present invention. The negative electrode may comprise ametal hydride active material. Alternately, the negative electrode maycomprise a cadmium active material.

EXAMPLE

A "standard" positive electrode paste was formed from about 88.6% activenickel hydroxide material, about 5% cobalt, about 6% cobalt oxide, andabout 0.4% polyvinyl alcohol binder. The paste was affixed to a nickelfoam substrate to form a "standard" positive electrode.

Three additional positive electrode pastes were formed by replacingabout 3% by weight of the nickel hydroxide material with the additives(1) bastnasite mineral, (2) bastnasite concentrate, and (3) MmNi₅. Thepastes were applied to nickel foam substrate to form (1) bastnasitemineral, (2) bastnasite concentrate, and (3) MmNi₅ positive electrodes.

The standard positive electrode as well as the three additionalelectrodes made from the new active materials were all tested using thetri-electrode test technique. A small tri-electrode cell for testingelectrodes was designed. The cell was fabricated by positioning apositive electrode between two negatives in the presence of excesselectrolyte. The three electrode system was held in place by twoplexiglass plates. The negative electrode used for the test was anickel-metal hydride electrode. After initial formation, charges weredone at C/10 to 120% charge. The discharges are done at C/10 untilcutoff voltage of 0.9 volts. The capacity of each electrode was measuredat 22° C. and at 45° C. The percentage decrease in capacity at 45° C.compared to that at 22° C. is shown in the Table.

                  TABLE                                                           ______________________________________                                        Additive       % decrease in capacity                                         ______________________________________                                        standard       16.0                                                             bastnasite ore 7.5                                                            bastnasite mineral 7.5                                                        MmNi.sub.5 10.2                                                             ______________________________________                                    

It is to be understood that the disclosure set forth herein is presentedin the form of detailed embodiments described for the purpose of makinga full and complete disclosure of the present invention, and that suchdetails are not to be interpreted as limiting the true scope of thisinvention as set forth and defined in the appended claims.

We claim:
 1. An active material mixture for use in a paste forfabricating positive electrodes, comprising:a nickel hydroxide material;and an additive material comprising at least one material selected fromthe group consisting of a rare earth mineral, and a rare earthconcentrate.
 2. The active material of claim 1, wherein said rare earthmineral is selected from the group consisting of bastnasite, monazite,loparite, xenotime, apatite, eudialyte, and brannerite.
 3. The activematerial of claim 1, wherein said rare earth concentrate is selectedfrom the group consisting of bastnasite concentrate, monaziteconcentrate, loparite concentrate, xenotime concentrate, apatiteconcentrate, eudialyte concentrate, and brannerite concentrate.
 4. Theactive material of claim 2, wherein said rare earth mineral is selectedfrom the group consisting of bastnasite, and monazite.
 5. The activematerial of claim 3, wherein said rare earth concentrate is selectedfrom the group consisting of bastnasite concentrate, and monaziteconcentrate.
 6. The active material of claim 1, wherein said rare earthmineral is heat treated.
 7. A nickel positive electrode for an alkalineelectrochemical cell, comprising:an active material mixture comprising:anickel hydroxide material; and an additive material comprising at leastone material selected from the group consisting of a rare earth mineral,and a rare earth concentrate.
 8. The positive electrode of claim 7,wherein said rare earth mineral is selected from the group consisting ofbastnasite, monazite, loparite, xenotime, apatite, eudialyte, andbrannerite.
 9. The positive electrode of claim 7, wherein said rareearth concentrate is selected from the group consisting of bastnasiteconcentrate, monazite concentrate, loparite concentrate, xenotimeconcentrate, apatite concentrate, eudialyte concentrate, and branneriteconcentrate.
 10. The positive electrode of claim 8, wherein said rareearth mineral is selected from the group consisting of bastnasite, andmonazite.
 11. The positive electrode of claim 9, wherein said rare earthconcentrate is selected from the group consisting of bastnasiteconcentrate, and monazite concentrate.
 12. The positive electrode ofclaim 7, wherein said rare earth mineral is heat treated.
 13. Analkaline electrochemical cell, comprising:at least nickel positiveelectrode; at least one negative electrode; and electrolyte; where saidpositive electrode comprising an active material mixture comprising:anickel hydroxide material; and an additive material comprises at leastone element selected from the group consisting of a rare earth mineral,and a rare earth concentrate.
 14. The electrochemical cell of claim 13,wherein said rare earth mineral is selected from the group consisting ofbastnasite, monazite, loparite, xenotime, apatite, eudialyte, andbrannerite.
 15. The electrochemical cell of claim 13, wherein said rareearth concentrate is selected from the group consisting of bastnasiteconcentrate, monazite concentrate, loparite concentrate, xenotimeconcentrate, apatite concentrate, eudialyte concentrate, and branneriteconcentrate.
 16. The electrochemical cell of claim 14, wherein said rareearth mineral is selected from the group consisting of bastnasite, andmonazite.
 17. The electrochemical cell of claim 15, wherein said rareearth concentrate is selected from the group consisting of bastnasiteconcentrate, and monazite concentrate.
 18. The electrochemical cell ofclaim 13, wherein said rare earth mineral is heat treated.
 19. Theelectrochemical cell of claim 13, wherein said negative electrodecomprises a metal hydride active material.
 20. The electrochemical cellof claim 13, wherein said negative electrode comprises a cadmium activematerial.